Atomic layer deposition using photo-enhanced bond reconfiguration

ABSTRACT

An atomic layer deposition process that reduces defective bonds formed when depositing atomic layers on a substrate or atomic layer when forming an integrated circuit device. As the layers are formed, a substrate or previous layer is exposed to a first reactant. After the substrate or layer has reacted with the first reactant, the substrate or layer is exposed to a second reactant. During or after exposure to the second reactant, electromagnetic radiation is applied to the substrate or layer. The electromagnetic radiation excites any defective bonds that may form in the deposition process to an energy level high enough to cause the elements forming the defective bonds to react with other elements contained in the second reactant. The reaction forms desirable bonds which attach to the substrate or previous layer to form an additional new layer.

FIELD

Atomic layer deposition.

BACKGROUND

Atomic layer deposition (ALD) is a deposition technique used to coatvarious features in the manufacturing process of circuit devices. Tocoat features, a film is grown layer by layer by exposing the surface toalternating pulses of reactants, each of which undergoes a self-limitingreaction, generally resulting in controlled film thickness. Eachreactant exposure provides an additional atomic layer to previouslydeposited layers.

A film growth cycle generally consists of two pulses, each pulse beingseparated by purges. For oxide films, the substrate is first exposed toan oxidizing agent which results in oxygen bonding with the surface ofthe substrate or previous layer.

In the ideal case, the exposed surface fully reacts with the oxidizingagent, but not with itself. Next, a reactant is exposed to the surface.The reactant reacts with the previous layer to form a single atomiclayer directly bonded to the underlying surface. Finally, an oxygencontaining species is exposed to the substrate, which reacts with thereactant to form a finished layer.

The film growth cycle may be repeated as many times as necessary toachieve a desired film thickness. In theory, each deposited layer formedby this process is defect free. However, the practical aspects of ALD donot necessarily lead to such defect-free films in which all of the bondsare fully formed.

BRIEF DESCRIPTION OF THE DRAWINGS

Various embodiments are illustrated by way of example and not by way oflimitation in the figures of the accompanying drawings in which likereferences indicate similar elements.

FIG. 1 shows a substrate, in one embodiment, being exposed to a firstreactant.

FIG. 2 shows the substrate of FIG. 1 in a hydroxyl-saturated state on afirst surface.

FIG. 3 shows the substrate of FIG. 2 purged of the first reactant.

FIG. 4 shows the substrate of FIG. 3 being exposed to a second reactantand electromagnetic radiation.

FIG. 5 shows a rastering configuration.

FIG. 6 shows the substrate of FIG. 4 in a reactant-saturated state.

FIG. 7 shows the substrate of FIG. 6 purged of the reactant.

FIG. 8 shows the substrate of FIG. 7 exposed to a third reactant andelectromagnetic radiation.

FIG. 9 shows the substrate of FIG. 8 in a hydroxyl-saturated state on asecond surface.

FIG. 10 shows the substrate of FIG. 9 purged of the reactant and formingan atomic layer.

FIG. 11 shows an atomic layer, in one embodiment, being exposed to afourth reactant.

FIG. 12 shows the atomic layer of FIG. 11 in a reactant-saturated state.

FIG. 13 shows the atomic layer of FIG. 12 purged of the reactant.

FIG. 14 shows the atomic layer of FIG. 13 being exposed to a fifthreactant.

FIG. 15 shows the atomic layer of FIG. 14 in a hydroxyl-saturated state.

FIG. 16 shows the atomic layer of FIG. 15 purged of the reactant andforming a second atomic layer.

DETAILED DESCRIPTION

FIG. 1 shows a semiconductor substrate such as a portion of asemiconductor wafer (e.g., silicon wafer). Substrate 100 may also beformed of gallium arsenide or any other material suitable for use as asemiconductor substrate (e.g., semiconductor on insulator structure).Reference to a silicon substrate will be made herein.

FIG. 1 shows substrate 100 being exposed to a first reactant in theformation of a binary metal oxide dielectric layer on surface 102 ofsubstrate 100. First reactant 150, in one embodiment, is an oxygensource. In the embodiment shown in FIG. 1, first reactant 150 is water(H₂O). Other suitable oxygen sources include, but are not limited to,oxygen gas, ozone, peroxide and ammonium hydroxide (NH₄OH).

In FIG. 1, as substrate 100 is exposed to first reactant 150, substrate100 reacts with first reactant 150 to form hydroxyl moieties (OH) 155 onsurface 102 of substrate 100. In another embodiment, first reactant 150is ammonia (NH₃). In embodiments where first reactant 150 is ammonia,NH₂ molecules form on surface 102 of substrate 100.

FIG. 2 shows substrate 100 in a hydroxyl-saturated state. Hydroxylsaturation occurs when the surface of substrate 100 becomes saturatedwith hydroxyl moieties 155. Representatively, to achieve ahydroxyl-saturated state on a silicon substrate, substrate 100 isexposed to first reactant 150 for about 0.1 to about 300 seconds and maybe exposed by way of submersing substrate 100 into a bath, sprayingfirst reactant 150 over the surface of substrate 100, or any othermethod that substantially exposes substrate 100 to first reactant 150.As described, the reaction between substrate 100 and first reactant 150is self-limiting in that there is limited available silicon with whichfirst reactant 150 may react. Therefore, increasing the exposure ofsubstrate 100 to first reactant 150 beyond a time period of completesaturation is acceptable.

FIG. 3 shows substrate 100 in a hydroxyl-saturated state after purgingthe reactant. Once hydroxyl saturation is achieved, substrate 100 isremoved from the reactant-containing environment and may be dried.

FIG. 4 shows hydroxyl-saturated substrate 100 being exposed to a secondreactant and electromagnetic radiation. In one embodiment, secondreactant 165 is a metal-containing substance or compound (e.g., a salt).In the embodiment shown in FIG. 4, second reactant 165 is zirconiumtetrachloride (ZrCl₄). Other suitable reactant substances include, butare not limited to, salts (e.g., chloride salts, fluoride salts, bromidesalts, iodide salts, etc.) of titanium, aluminum, gallium, cesium,indium, hafnium, tantalum, praseodymium, niobium, scandium, lutetium,cerium and lanthanum. Second reactant 165, in general, is a metalchloride or any other suitable metal-containing substance or compound.

Hydroxyl-saturated substrate 100 is exposed to second reactant 165 byimmersing substrate 100 into a bath containing second reactant 165,spraying second reactant 165 over the surface of substrate 100, or anyother method that substantially exposes substrate 100 to second reactant165. As hydroxyl-saturated substrate 100 is exposed to second reactant165, hydroxyl moieties 155 on surface 102 of substrate 100 begin toreact with second reactant 165 to form, in one embodiment, SiOZrCl₃molecules 160 on surface 102 of substrate 100 and free hydrochloric acid(HCl) 175. It is also possible for second reactant 165 to react with twohydroxyl moieties 155 to form O₂ZrCl₂ molecule 180 while releasing twoequivalents of HCl 175.

Hydrochloric acid 175 is either in a liquid or gaseous state and isdispersed away from substrate 100 by a purge gas or vacuum in a chamber.Representatively, in a typical process to predominately or completelyreact hydroxyl moieties 155 with second reactant 165, substrate 100 is,for example, placed in an immersion bath for about 0.1 to about 300seconds. As described, the reaction between hydroxyl moieties 155 andsecond reactant 165 is self-limiting in that there is limited availablehydroxyls with which second reactant 165 may react. Therefore,increasing the exposure of substrate 100 to second reactant 165 beyond atime period of complete saturation is acceptable.

During the reaction of hydroxyl moieties 155 and second reactant 165,dangling bonds and reactant bonds can form. Dangling bonds occur when areactant element, Zr in this example, bonds with another reactantelement, Zr, instead of, in one case, an oxygen atom when forming anatomic layer film on a surface. Reactant bonds occur when a reactantcompound, ZrCl₄ in this example, does not fully react with a reactantbut instead bonds with desired bonds, Zr—O, to form Zr—Cl bonds in anALD film layer.

During the early stages of film nucleation, dangling bonds and reactantbonds can alter the atomic configuration of the film and result inislanding and poor film growth. In addition, dangling bonds and reactantbonds inhibit the formation of subsequently deposited atomic layers.

To reduce or minimize the number of these defective bonds, substrate 100is exposed to electromagnetic radiation 145 after hydroxyl/reactant bondformation. Substrate 100 may be exposed to electromagnetic radiationeither while being exposed to second reactant 165, after removal ofsubstrate 100 from a second reactant 165—containing environment, or bothduring exposure to second reactant 165 and after removal from a secondreactant 165—containing environment. As defective bonds are exposed toelectromagnetic radiation 145, the defective bonds become excited andrise to a greater energy level.

When the bonds reach an activation energy level, the bonds are in astate where they tend to seek out other elements with which to form newbonds. Thus, the electromagnetic radiation at the proper wavelengthmodifies the reaction kinetics to encourage the destruction of defectivebonds and the formation of desirable bonds. For example, since theactivation energy for the conversion of surface —ZrCl_(x) to surface—ZrCl_(x-1)(OH) is approximately +1.6 kcal/mole, a photon-emittingdevice may be used to expose the target area to a wavelength that willcause energy levels to gain at least +1.6 kcal/mole. In one embodiment,the energy required to activate a reactant and/or dangling bond isinsufficient to activate a desired bond (e.g., a Zr—O bond).

In one embodiment, electromagnetic radiation is supplied by a tunablelaser. The tunable laser, in one embodiment, is a dye laser. In anembodiment where substrate 100 is a wafer, one technique for exposingsubstrate 100 to an electromagnetic radiation source is by revolving thewafer in the presence of a dye laser. The dye laser emits pulses ofradiation onto the wafer along circular revolutions or rasters becomingsubsequently larger or smaller as the laser is advanced from either acenter or edge of the wafer, respectively. In one embodiment, arastering speed is selected such that one or more pulses of a dye laser,for example, deliver sufficient energy to substrate 100 to activateundesired bonds (e.g., to deliver an energy to an undesired bond equalto or greater than an activation energy for the bond).

The selection of the wavelength of light depends on the type of defectencountered. In one embodiment, electromagnetic radiation 145 istargeted to an area of the electromagnetic spectrum wherein thedefective bonds will become strongly excited, but the desired chemicalbonds will remain unaffected. In one example, undesirable bonds such asZr—Cl or Zr—Zr bonds in an ALD process for ZrO₂ formation would betargeted for a process using an oxygen source or a reactant such as H₂Oand ZrCl₄, respectively. In this example, the desired bonds in thematrix would include Si—O bonds near the substrate surface and Zr—Obonds in subsequent layers.

FIG. 5 shows a rastering configuration for exposing defect bonds toelectromagnetic radiation. In this configuration, wafer 510 is on apedestal or similar stag that can be rotated. Laser 500 scans across thesurface of wafer 510 to remove any defective bonds. Laser 500 isadjustable such that laser 500 can emit wavelengths of light atpre-determined frequencies. Thus, wafer 510, and any defective bondsthat may exist on wafer 510 in the dielectric layer, are exposed toenough electromagnetic radiation to excite the defective bonds as laser500 scans across wafer 510.

FIG. 6 shows substrate 100 in a reactant-saturated state. In this state,the surface of substrate 100 containing SiOH bonds has reacted with thereactant to form SiOZrCl₃ molecules 160 on the surface of substrate 100.

FIG. 7 shows the surface of substrate 100 saturated with SiOZrCl₃molecules 160 after removal of the reactant and HCl. After surface 102of substrate 100 is saturated with SiOZrCl₃ molecules 160, substrate 100is removed from the reactant-containing environment and possibly dried.After substrate 100 is dried, SiOZrCl₃ molecule-saturated substrate 100is exposed to another reactant.

FIG. 8 shows SiOZrCl₃ molecule-saturated substrate 100 being exposed toa third reactant and electromagnetic. In one embodiment, third reactant250 is an oxygen source. In another embodiment, third reactant 250 isammonia. In the embodiment shown in FIG. 8, the oxygen source is H₂O.Other suitable oxygen sources include, but are not limited to, oxygengas, ozone, peroxide and ammonium hydroxide.

In the embodiment shown in FIG. 8, when SiOZrCl₃ molecules 160 onsurface 102 of substrate 100 are exposed to third reactant 250, areaction occurs forming SiOZr(OH)Cl₂ molecules 255 on surface 102 ofsubstrate 100 and free HCl molecules 275. In embodiments where thirdreactant 250 is ammonia, a reaction occurs forming SiNZrCl₂NH₂ moleculeson surface 102 of substrate 100 and free HCl molecules 275.

Hydrochloric acid 275 is either in a liquid or gaseous state and isdispersed away from substrate 100 by a purge gas or vacuum in a chamber.Representatively, in a typical process to predominately or completelyreact SiOZr(OH)Cl₂ molecules 255 with third reactant 250, substrate 100is, for example, placed in an immersion bath or sprayed for about 0.1 toabout 300 seconds. As described, the reaction between SiOZrCl₃ molecules160 and third reactant 250 is self-limiting in that there is limitedavailable SiOZrCl₃ molecules 160 with which third reactant 250 mayreact. Therefore, increasing the exposure of substrate 100 to thirdreactant 250 beyond a time period of complete saturation is acceptable.

To reduce or minimize the number of defective bonds, substrate 100 isexposed to electromagnetic radiation 245 after hydroxyl bond formation.Electromagnetic radiation 245 may be any of the embodiments similar toelectromagnetic radiation 145 discussed above.

Substrate 100 may be exposed to electromagnetic radiation 245 eitherwhile being exposed to third reactant 250, after removal of substrate100 from a third-reactant 250-containing environment, or both duringexposure to third reactant 250 and after removal from a third reactant250-containing environment. As defective bonds are exposed toelectromagnetic radiation 245, the defective bonds become excited andrise to a greater energy level.

When the bonds reach an activation energy level, the bonds are in astate where they tend to seek out other elements with which to form newbonds. Thus, the electromagnetic radiation at the proper wavelengthmodifies the reaction kinetics to encourage the destruction of defectivebonds and the formation of desirable bonds. For example, since theactivation energy for the conversion of surface —ZrCl_(x) to surface—ZrCl_(x-1)(OH) is approximately +1.6 kcal/mole, a photon-emittingdevice may be used to expose the target area to a wavelength that willcause energy levels to gain at least +1.6 kcal/mole. In one embodiment,the energy required to activate a reactant and/or dangling bond isinsufficient to activate a desired bond (e.g., a Zr—O bond).

FIG. 9 shows the surface of substrate 100 after third reactant 250 hasfully reacted with the SiOZrCl₃ molecules. After the SiOZrCl₃ moleculeshave fully reacted with third reactant 250, the surface of substrate 100becomes saturated with SiOZr(OH)₃ molecules 260 while forming additionalfree HCl molecules in a reaction represented by the equations:SiOZr(OH)Cl₂+2 H₂O→SiOZr(OH)₃+2HClSiOZr(OH)₂Cl+SiOZr(OH)₃→SiOZr(OH)₂-μO—(OH)₂ZrOSi+HCl

FIG. 10 shows a finished first atomic layer formed by an ALD processafter substrate 100 has been removed from the reactant-containingenvironment. In this example, atomic layer 105 is formed of zirconiumoxide (ZrO₂) molecules 270 having hydroxyl moieties 255 bonded to ZrO₂molecules 270. Atomic layer 105 is now prepared and capable of having anatomic layer formed upon it.

FIG. 11 shows atomic layer 105 being exposed to a fourth reactant. Inone embodiment, fourth reactant 265 is a metal-containing substance orcompound (e.g., a salt). In the embodiment shown in FIG. 11, fourthreactant 265 is zirconium chloride. Other suitable reactant substancesand compounds include, but are not limited to, salts (e.g., chloridesalts, fluoride salts, bromide salts, iodide salts, etc.) of titanium,aluminum, gallium, cesium, indium, hafnium, tantalum, praseodymium,niobium, scandium, cerium, lutetium and lanthanum. Fourth reactant 265,in general, is a metal chloride or any other suitable metal-containingsubstance.

Layer 105 is exposed to fourth reactant 265 by immersing layer 105 intoa bath containing fourth reactant 265, spraying fourth reactant 265 oversurface 107 of layer 105, or any other method that substantially exposeslayer 105 to fourth reactant 265. The exposure time should be longenough to maximize the reaction between layer 105 and fourth reactant265. In one embodiment, layer 105 is exposed to fourth reactant 265 forabout 0.1 to about 300 seconds, but because the reaction isself-limiting, a longer exposure time will not adversely affectdielectric layer formation.

As layer 105 is exposed to fourth reactant 265, the hydroxyl moieties255 on surface 107 of layer 105 begin to react with fourth reactant 265to form, in this embodiment, ZrOZrCl₃ molecules 260 on surface 107 oflayer 105 and free hydrochloric acid 275. Hydrochloric acid 275 iseither in a liquid or gaseous state and is dispersed away from layer 105by a purge gas or vacuum in a chamber. Representatively, in a typicalprocess to predominately or completely react hydroxyls 255 with fourthreactant 265, layer 105 is, for example, placed in an immersion bath orsprayed for about 0.1 to about 300 seconds. As described, the reactionbetween hydroxyl moieties 255 and fourth reactant 265 is self-limitingin that there is limited available hydroxyls with which fourth reactant265 may react. Therefore, increasing the exposure of layer 105 to fourthreactant 265 beyond a time period of complete saturation is acceptable.

During the reaction of hydroxyl moieties 255 and fourth reactant 265dangling and reactant bonds can form. To reduce or minimize the numberof these defective bonds, layer 105 is exposed to electromagneticradiation 245. Layer 105 may be exposed to electromagnetic radiationeither while being exposed to fourth reactant 265, after removal oflayer 105 from a fourth reactant 265-containing environment, or bothduring exposure to fourth reactant 265 and after removal from a fourthreactant 265-containing environment. In one embodiment, layer 105 isexposed to electromagnetic radiation 245 for about 0.1 to about 180seconds. As the defective bonds are exposed to electromagnetic radiation245, the defective bonds become excited and rise to a greater energylevel.

Sufficient exposure to electromagnetic radiation 245 during, after orboth during and after exposure to fourth reactant 265 allows layer 105to become substantially defect-free. Layer 105 is substantially defectfree because defective bonds that may have formed are excited by theelectromagnetic radiation to a higher energy level causing the defectbonds to be more likely to react with a precursor to form non-defectivesites, in this case, Zr—O bonds on the substrate. Thus, defect bonds arereduced or minimized since the reaction essentially replaces theundesired bonds on the layer with desirable bonds.

FIG. 12 shows layer 105 in a reactant-saturated state. In this state,surface 107 of layer 105 containing ZrO(OH) bonds has reacted with thereactant to form ZrOZrCl₃ 260 molecules on surface 107 of layer 105

FIG. 13 shows surface 107 of layer 105 saturated with ZrOZrCl₃ molecules260 after purging the reactant. After surface 107 of layer 105 issaturated with ZrOZrCl₃ molecules 260, layer 105 is removed from thereactant-containing environment and possibly dried. After layer 105 isdried, ZrOZrCl₃ molecule-saturated layer 105 is exposed to anotherreactant.

FIG. 14 shows ZrOZrCl₃ molecule-saturated layer 105 being exposed to afifth reactant. In one embodiment, fifth reactant 350 is an oxygensource. In another embodiment, fifth reactant 350 is ammonia. In theembodiment shown in FIG. 14, the oxygen source is H₂O. Other suitableoxygen sources include, but are not limited to, oxygen gas, ozone,peroxide and ammonium hydroxide.

In this embodiment, when ZrOZrCl₃ molecules on surface 107 of layer 105are exposed to fifth reactant 350, a reaction occurs formingZrOZr(OH)Cl₂ molecules 355 on surface 107 of layer 105 and free HClmolecules 375. In embodiments where third reactant 250 is ammonia, areaction occurs forming ZrNZrCl₂NH₂ molecules on surface 107 of layer105 and free HCl molecules 375.

Hydrochloric acid 375 is either in a liquid or gaseous state and isdispersed away from layer 105 by a purge gas or vacuum in a chamber.Representatively, in a typical process to predominately or completelyreact ZrOZrCl₃ molecules with fifth reactant 350, layer 105 is, forexample, placed in an immersion bath or sprayed for about 0.1 to about300 seconds. As described, the reaction between ZrOZrCl₃ molecules andfifth reactant 350 is self-limiting in that there is limited availableZrOZrCl₃ molecules with which fifth reactant 350 may react. Therefore,increasing the exposure of layer 105 to fifth reactant 350 beyond a timeperiod of complete saturation is acceptable.

FIG. 15 shows the surface of layer 105 after fifth reactant 350 hasfully reacted with the ZrOZrCl₃ molecules. After the ZrOZrCl₃ moleculeshave fully reacted with fifth reactant 350, surface 107 of layer 105 hasbecome saturated with ZrOZr(OH)₃ molecules 355 while forming additionalfree HCl molecules in a reaction represented by the equations:ZrOZr(OH)Cl₂+2 H₂O→ZrOZr(OH)₃+2HClZrOZr(OH)₂Cl+ZrOZr(OH)₃→ZrOZr(OH)₂-μO—(OH)₂ZrOZr+HCl

FIG. 16 shows a finished second atomic layer formed by an ALD processafter layer 105 has been removed from the reactant-containingenvironment. Second layer 110 is formed of ZrO molecules 370 having OHmolecules 355 bonded to ZrO molecules 370. Layer 110 is now prepared andcapable of having an atomic layer formed upon it.

The process of forming individual layers upon previous layers may berepeated until the number of desired layers and/or film thickness isreached. As each layer is deposited without defects, overall deviceintegrity and manufacturing yield increases.

In the foregoing specification, the invention has been described withreference to specific embodiments thereof. It will, however, be evidentthat various modifications and changes can be made thereto withoutdeparting from the broader spirit and scope of embodiments of theinvention as set forth in the appended claims. The specification anddrawings are, accordingly, to be regarded in an illustrative rather thana restrictive sense.

1. A method, comprising: exciting an undesirable bond in an atomic layerdeposition (ALD) formed film to an energy level greater than a groundstate of the undesirable bond.
 2. The method of claim 1, furthercomprising: after exciting the undesirable bond, exposing the film to areactant.
 3. The method of claim 2, wherein the reactant is an oxygensource.
 4. The method of claim 3, wherein the oxygen source is water. 5.The method of claim 2, wherein the reactant comprises a metal precursor.6. The method of claim 5, wherein the metal is one of zirconium,titanium, aluminum, gallium, cesium, indium, haffium, tantalum,praseodymium, niobium, scandium, lutetium, cerium and lanthanum.
 7. Themethod of claim 1, wherein the undesirable bonds are metal-metal bonds.8. The method of claim 7, wherein the metal is selected from a groupconsisting of zirconium, titanium, aluminum, gallium, cesium, indium,hafnium, tantalum, praseodymium, niobium, scandium, lutetium, cerium andlanthanum.
 9. The method of claim 1, wherein the film is a metal oxidefilm.
 10. The method of claim 1, wherein exciting the undesirable bondscomprises exposing the undesirable bonds to electromagnetic radiation.11. A method, comprising: forming a film on a substrate, wherein formingthe film comprises: exposing the substrate to a reactant to formhydroxyl bonds on a surface of the substrate; exposing the hydroxylbonds to a reactant; and applying an electromagnetic radiation to thehydroxyl bonds while the hydroxyl bonds are exposed to themetal-containing reactant, the radiation of a sufficient magnitude toexcite undesirable bonds formed during the exposure of the hydroxylbonds to the reactant.
 12. The method of claim 11, wherein the reactantis an oxygen source
 13. The method of claim 12, wherein the oxygensource is water.
 14. The method of claim 11, wherein the reactantincludes a metal selected from a group consisting of zirconium,titanium, aluminum, gallium, cesium, indium, hafnium, tantalum,praseodymium, niobium, scandium, lutetium, cerium and lanthanum.
 15. Themethod of claim 11, wherein the electromagnetic radiation is applied bya tunable laser.
 16. The method of claim 11, wherein the undesirablebonds are metal to metal bonds.
 17. The method of claim 16, wherein themetal is selected from a group consisting of zirconium, titanium,aluminum, gallium, cesium, indium, hafnium, tantalum, praseodymium,niobium, scandium, lutetium, cerium and lanthanum.
 18. The method ofclaim 11, wherein the undesirable bonds are metal to halide bonds. 19.The method of claim 11, wherein the film formed on the substrate is ametal oxide.
 20. The method of claim 11, wherein the film formed on thesubstrate is a metal nitride.
 21. A method, comprising: modifyingundesirable bonds in an atomic layer deposition (ALD) formed film to anenergy level greater than a ground state of the undesirable bonds; andexposing the film to a reactant.
 22. The method of claim 21, whereinmodifying the undesirable bonds comprises reducing the number ofundesirable bonds on the film.
 23. The method of claim 21, whereinmodifying the undesirable bonds comprises minimizing the number ofundesirable bonds on the film.